本文選題：芳乙烯基　切入點：長鏈柔性二羧酸　出處：《重慶師范大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：功能性金屬-有機超分子聚合物得到了國內(nèi)外科學(xué)家的高度重視,不僅因為其新穎的結(jié)構(gòu),而且在發(fā)光、催化、氣體存儲、分離等方面都具有潛在的應(yīng)用價值。含芳乙烯基的柔性二羧酸或多羧酸因為多樣的構(gòu)象和配位模式,以及苯環(huán)π-π疊加、氫鍵等相互作用,有利于獲得具有穿插、螺旋、纏繞等結(jié)構(gòu)的功能超分子聚合物。然而,這類羧酸配體在超分子化學(xué)領(lǐng)域還沒有得到深入開發(fā)。本論文用含芳乙烯基的長鏈柔性羧酸1,3-(2-丙烯酸基苯氧基)丙烷(H2ppa)作為O-配體。以不同聯(lián)吡啶配體,1,2-bi(4-pyridyl)ethylene(簡寫為bpe),1,4-bis[2-(4-pyridyl)ethenyl]benzene(簡寫為bpeb),4,4'-bis[2-(4-pyridyl)ethenyl]biphenyl(簡寫為bpep),2,2-bipyridine(簡寫為2,2’-bpy)和4,4-bipyridine(簡寫為4,4’-bpy)作為N-配體。在溶劑熱條件下,O-配體、N-配體分別與不同的d10過渡金屬鹽組裝了八個新的超分子化合物,其組成分別為{[Zn4(bpe)3(ppa)4](H2O)6}n(1)、[Cd(ppa)(bpe)]n(2)、[Zn2(ppa)2(bpeb)]n(3)、[Co2(ppa)2(bpeb)](4)、[Zn2(ppa)2(bpep)]n(5)、[Zn(Hppa)2(2,2’-bpy)](H2O)(6)、[Zn2(ppa)2(4,4’-bpy)]n(7)和[Co2(ppa)2(4,4’-bpy)]n(8),其中化合物3與4、7與8分別為同構(gòu)化合物。實驗過程中,我們探究了溶液pH值、溶劑、溫度、反應(yīng)物配比等因素對超分子組裝的影響。通過X-射線單晶衍射、紅外、X-粉末衍射等手段對制備的超分子化合物進行表征和分析,測定化合物的熱穩(wěn)定性,研究了發(fā)光性能。X-射線單晶衍射揭示出,化合物1-5中存在著左右兩種不同螺旋結(jié)構(gòu)的一維鏈�；衔�1,3,5是層狀(2D)配位聚合物,并通過互鎖形成了三維(3D)超分子結(jié)構(gòu)。柔性配體ppa2-在這些化合物中呈現(xiàn)出不同的構(gòu)型和不同的配位方式。同時在化合物1和3的互鎖區(qū)域,兩種不同的左手螺旋和右手螺旋結(jié)構(gòu)交替排列�；衔�5中,存在18.98?×16.27?維度納米尺寸的環(huán),相鄰的二維層,進一步的互鎖形成三維(3D)超分子結(jié)構(gòu)。在化合物1,3,5中,O-配體ppa存在著不同的配位模式和構(gòu)象�；衔�2中,螺旋子通過共享金屬離子形成了左手螺旋和右手螺旋結(jié)構(gòu)(其交替排列在層狀結(jié)構(gòu)的兩側(cè)),并通過含氮配體進一步構(gòu)筑了三維的配位超分子結(jié)構(gòu)。化合物6是類似英文字母“W”的零維結(jié)構(gòu),進一步通過氫鍵構(gòu)筑的二維網(wǎng)狀超分子化合物,而化合物7也是含螺旋結(jié)構(gòu)的柱撐的三維配位超分子化合物。論文研究了新超分子化合物的熒光性能,并探討了熒光性質(zhì)與相應(yīng)電子結(jié)構(gòu)之間的關(guān)系。上述的結(jié)構(gòu)和性質(zhì),揭示了長鏈柔性羧酸,有利于組裝螺旋、互鎖等結(jié)構(gòu)的超分子化合物,共軛的芳乙烯基的有利于得長波光敏性能。
[Abstract]:Functional metal-organic supramolecular polymers have attracted great attention from scientists at home and abroad, not only because of their novel structure, but also because of their luminescence, catalysis and gas storage. The flexible dicarboxylic acid or polycarboxylic acid containing aryl vinyl group is advantageous to the intercalation and helix because of its various conformation and coordination modes, as well as the interaction of benzene 蟺-蟺 superposition and hydrogen bond. Functional supramolecular polymers with structures such as winding. However, This kind of carboxylic acid ligands have not been further developed in the field of supramolecular chemistry. In this thesis, a long chain flexible carboxylic acid containing aryl vinyl group, 1 / 3-(2-(acrylic) phenoxy) propane (H _ 2ppa), was used as an Oligand. Different bipyridine ligands were used as Oligand with different bipyridine ligands: 1 / 2-bipyridylethylene. Benzene14-bis [2-Py 4-pyridylethenyl] benzene- bis [2-4-pyridylethenyl] biphenyl- (abbreviated as bpeptio 22-bipyridine (22-bpyine) and 44-bipyridine (44-bipyridine-4bpy4) as N-ligand. Eight new supramolecular compounds were assembled under solvothermal conditions, respectively, with different D10 transition metal salts. Their compositions are {[Zn4(bpe)3(ppa)4] H _ 2O _ 2 ~ (6)} n ~ (1), [CD _ (2) PPA ~ (2 +) ~ (2 +))] ~ (2) N ~ (2 +), [Zn _ (2) PPA _ (2) B _ (peb))] n ~ (7), [[Co _ (2) PPA _ (2) H _ 2O _ (2) B _ (peb))] _ (4), [[Co _ (2) PPA _ (2) H _ 2O _ (2) B _ (P))] ~ (2) ~ (1), [[Zn _ (2) Zn4(bpe)3(ppa)4] ~ (2) H _ 2O _ (2) B _ (p) ~ (2) H _ 2O _ (2) H _ 2O _ (2) H _ (2) H _ (2) H _ (2) H _ (2) O _ (2) H _ (2) O _ (1), [[Zn _ (2) PPA _ (2) PPA _ (2) O _ (2) B _ (PY))]? The effect of reactant ratio on supramolecular assembly. The supermolecular compounds were characterized and analyzed by means of X-ray single crystal diffraction and infrared X-ray powder diffraction to determine the thermal stability of the compounds. The photoluminescence properties. X- ray single crystal diffraction revealed that there are two different helical chains in compound 1-5. Compound 1: 3 (5) is a lamellar 2D) coordination polymer. The flexible ligand ppa2- presents different configurations and different coordination modes in these compounds. At the same time, the interlocking regions of compounds 1 and 3 are found. Two different spiral structures of left hand and right hand are arranged alternately. In compound 5, 18.98? 脳 16.27? Dimensional nanoscale rings, adjacent two-dimensional layers, and further interlocking to form a three-dimensional (3D) supramolecular structure. In compound 1, 3, 5, there are different coordination modes and conformations for the ligand ppa. In compound 2, Helicons form left-handed and right-hand spiral structures by sharing metal ions, which alternately arrange on both sides of the layered structure, and further construct a three-dimensional coordination supramolecular structure through nitrogen-containing ligands. Compound 6 is analogous. The zero-dimensional structure of the English letter "W", Furthermore, 2-D network supramolecular compounds were constructed by hydrogen bonding, and compound 7 was also a three-dimensional coordination supramolecular compound with helical structure. The fluorescence properties of new supramolecular compounds were studied in this paper. The relationship between the fluorescence properties and the corresponding electronic structures is discussed. The structure and properties above reveal that long chain flexible carboxylic acids are conducive to the assembly of supramolecular compounds with helical and interlocking structures. The conjugated aryl vinyl group is advantageous to the long wave Guang Min performance.
【學(xué)位授予單位】：重慶師范大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O641.4

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本文編號：1607797